- Unconventional reactivity of epichlorohydrin in the presence of triphenylphosphine: isolation of ((1,4-dioxane-2,5-diyl)-bis-(methylene))-bis-(triphenylphosphonium) chloride
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The selective formation of the heterocyclic salt ((1,4-dioxane-2,5-diyl)-bis-(methylene))-bis-(triphenylphosphonium) chloride was observed when epichlorohydrin and triphenylphosphine were reacted in CH2Cl2 at room temperature. Slow evaporation from a mixture of ethanol and ethyl acetate allows to isolate monocrystals of the heterocyclic phosphonium salt. Mechanistic investigations point to the formation of the zwitterionic intermediate 1-chloro-3-(triphenylphosphonio)-propan-2-olate, which can dimerize and generate the 1,4-dioxane derivative. In the exclusive presence of a Br?nsted acid as HCl, which usually facilitates epoxide ring opening, the exclusive formation of 1,3-dichloro-2-propanol was although observed. Also, when epichlorohydrin, PPh3, and a stoichiometric amount of HCl were mixed, (2-chloro-3-hydroxypropyl)-triphenylphosphonium chloride was formed and its isolation in pure form provides monocrystals subjectable to X-ray analysis.
- Mannu, Alberto,Di Pietro, Maria Enrica,Priola, Emanuele,Baldino, Salvatore,Sacchetti, Alessandro,Mele, Andrea
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-
Read Online
- A method for efficient preparation of epichlorohydrin by biomass glycerol
-
The present invention discloses a method for efficiently preparing epichlorohydrin by biomass glycerol, comprising the following steps: 1) the mass ratio of 1: 0.06 ~ 0.08 of biomass glycerol and a composite catalyst poured into the reactor, and then using an ultrasonic probe to extend into the reactor, 2) step 1) after the end of the reaction, the resulting material is cooled to room temperature and transferred to the reaction vessel, maintaining a temperature of 15 ~ 30 ° C, and then adding an alkaline cyclizer for the reaction; 3) after the completion of the reaction to filter the resulting solids, The filtrate is a solution of epichlorohydrin oxide; the glycerol of the present invention can be completely converted, the intermediate product dichloropropanol yield is high, and the selectivity of collecting 1,3-dichloropropanol is improved, which accelerates the reaction rate; and the process can be co-produced with biodiesel and chlor-alkali industry, and the industrialization prospect is good.
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Paragraph 0038-0039; 0049-0050; 0060-0061; 0073
(2022/01/10)
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- Preparation method for 1,3-propylene glycol from glycerol
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The invention relates to a preparation method for 1,3-propylene glycol from glycerol, wherein the preparation method comprises the steps of chlorohydrination reaction, cyclization reaction, hydrogenation reaction and the like. The glycerin conversion rate of the preparation method reaches 99% or above, the yield of 1,3-propylene glycol reaches 65% or above, and the preparation method has the advantages of being simple in process, mild in reaction condition, small in investment, high in technical safety and easy to operate and control.
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Paragraph 0066-0076
(2021/04/10)
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- Preparation method of sodium beta-glycerophosphate containing crystal water
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The invention discloses a preparation method of sodium beta-glycerophosphate containing crystal water. The method comprises the following steps: A) taking epoxy chloropropane as an initial raw material, slowly dropwise adding the epoxy chloropropane into hydrochloric acid, reacting for 1-6 hours, adjusting the pH value to 3-4 by using a sodium hydroxide solution, carrying out vacuum distillation to remove moisture, distilling to 60 DEG C, adding a drying agent, stirring for 1 hour, and filtering to obtain 1, 3-dichloropropanol; B) adding the 1,3-dichloropropanol into an esterification reactionkettle, adding a phosphating agent, heating the temperature to 80-130 DEG C, controlling the temperature to esterify for 10-20 hours, after esterification is finished, adding water for dilution, dropwise adding the sodium hydroxide solution, adjusting the pH value to be 9-13, keeping the temperature at 40-80 DEG C, hydrolyzing for 3-5 hours, adding magnesium oxide or calcium oxide and stirring for 2 hours at 60-80 DEG C, adding activated carbon and stirring for 1 hour, the negative pressure distillation concentration being 70%-75%, adding ethyl alcohol, carrying out cooling and stirring and filtering to obtain the sodium beta-glycerophosphate. According to the invention, the generation of sodium alpha-glycerophosphate is avoided, and the sodium beta-glycerophosphate containing crystal water and not containing crystal water can be flexibly prepared.
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Page/Page column 5-7
(2020/12/08)
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- Expeditious Syntheses to Pharmochemicals 1,3-Dihydroxyacetone, 1,3-Dichloro-, 1,3-Dibromo- And 1,3-Diiodoacetone from Glycerol 1,3-Dichlorohydrin Using Homogenous and Heterogenous Medium
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New efficient and reproductive routes to production of 1,3-dihydroxyacetone (1), 1,3-dichloroacetone (6), 1,3-dibromoacetone (7) and 1,3-diiodoacetone (8) from glycerol 1,3-dichlorohydrin (3) were developed. The synthesis of 1 was processed in three steps from glycerol 2 (1,3-selective chlorination of 2 to 3, oxidation of 3 to 6 and subsequent di-hydroxylation) in 51% overall yield. On the other hand, 7 and 8 were produced from 3, via a trans-bromination and trans-iodination, respectively, followed by oxidation and hydroxylation steps, in 38-52% overall yield. It was used homogeneous media with different reagents (HCl/AcOH, pyridinium chlorochromate (PCC), PCC-HIO4) and heterogeneous media with reagents supported on polymer resins such as Amberlyst A26-HCrO4– form, PV-PCC (polyvinyl-pyridinium chlorochromate) and Amberlyst A26-OH– form or reagents supported on alumina such as KI/Al2O3, KBr/Al2O3, in solvent free conditions.
- Pereira, Vera Lúcia P.,da Silva, Fernanda Priscila N. R.,da Silva, Sara R. B.,dos Santos, Priscila F.
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p. 1725 - 1731
(2020/10/09)
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- Laminaria digitata and palmaria palmata seaweeds as natural source of catalysts for the cycloaddition of CO2 to Epoxides
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Seaweed powder has been found to act as an effective catalyst for the fixation of CO2 into epoxides to generate cyclic carbonates under solvent free conditions. Model background reactions were performed using metal halides and amino acids typically found in common seaweeds which showed potassium iodide (KI) to be the most active. The efficacy of the seaweed catalysts kelp (Laminaria digitata) and dulse (Palmaria palmata) was probed based on particle size, showing that kelp possessed greater catalytic ability, achieving a maximum conversion and selectivity of 63.7% to styrene carbonate using a kelp loading of 80% by weight with respect to epoxide, 40 bar of CO2, 120?C for 3 h. Maximizing selectivity was difficult due to the generation of diol side product from residual H2O found in kelp, along with a chlorinated by-product thought to form due to a high quantity of chloride salts in the seaweeds. Data showed there was loss of organic matter upon use of the kelp catalyst, likely due to the breakdown of organic compounds and their subsequent removal during product extraction. This was highlighted as the likely cause of loss of catalytic activity upon reuse of the Kelp catalyst.
- Comerford, James W.,Gray, Thomas,Lie, Yann,Macquarrie, Duncan J.,North, Michael,Pellis, Alessandro
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- Continuous flow upgrading of glycerol toward oxiranes and active pharmaceutical ingredients thereof
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A robust continuous flow procedure for the transformation of bio-based glycerol into high value-added oxiranes (epichlorohydrin and glycidol) is presented. The flow procedure features a central hydrochlorination/dechlorination sequence and provides economically and environmentally favorable conditions involving an organocatalyst and aqueous solutions of hydrochloric acid and sodium hydroxide. Pimelic acid (10 mol%) shows an exceptional catalytic activity (>99% conversion of glycerol, a high selectivity toward 1,3-dichloro-2-propanol and 81% cumulated yield toward intermediate chlorohydrins) for the hydrochlorination of glycerol (140 °C) with 36 wt% aqueous HCl. These conditions are validated on a sample of crude bio-based glycerol. The dechlorination step is effective (quantitative conversion based on glycerol) with concentrated aqueous sodium hydroxide (20 °C) and can be directly concatenated to the hydrochlorination step, hence providing a ca. 2:3 separable mixture of glycidol and epichlorohydrin (74% cumulated yield). An in-line membrane separation unit is included downstream, providing usable streams of epichlorohydrin (in MTBE, with an optional concentrator) and glycidol (in water). The scalability of the dechlorination step is then assessed in a commercial pilot-scale continuous flow reactor. Next, bio-based epichlorohydrin is further utilized for the continuous flow preparation of β-amino alcohol active pharmaceutical ingredients including propranolol (hypertension, WHO essential), naftopidil (prostatic hyperplasia) and alprenolol (angina pectoris) within a concatenable two-step procedure using a FDA class 3 solvent (DMSO). This work provides the first example of direct upgrading of bio-based glycerol into high value-added pharmaceuticals under continuous flow conditions.
- Morodo, Romain,Gérardy, Romaric,Petit, Guillaume,Monbaliu, Jean-Christophe M.
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supporting information
p. 4422 - 4433
(2019/08/21)
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- Method for preparing 1,3-dichloro-2-propanol
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The present invention discloses a method for preparing 1,3-dichloro-2-propanol. The method comprises the following steps: performing a contact reaction on allyl chloride, hydrogen chloride, an oxidantand an oxygen-containing hydrocarbon in the presence of a catalyst, wherein the oxygen-containing hydrocarbon is an alcohol and/or a carboxylic acid, and the catalyst is a titanium silicate molecularsieve catalyst. The method has the advantages of no use of toxic chlorine, simple operation process, mild reaction conditions, high selectivity of 1,3-dichloro-2-propanol, and easy separation of thecatalyst.
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Paragraph 0051-0075
(2018/05/16)
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- Effect of sodium chloride on the solubility and hydrolysis of epichlorohydrin in water
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The mutual solubility of the components in the epichlorhydrin–water–sodium chloride system was studied in the temperature range of 20–90 °С. It was found that epichlorohydrin is salted out as the concentration of NaCl increases. The Sechenov coefficient was determined to be equal to 0.29. It was found that epichlorohydrin reacts with an aqueous solution of sodium chloride to form glycerol dichlorohydrins. Alkali formed during this reaction catalyzes the hydrolysis of epichlorohydrin to glycerol monochlorohydrin, acts as a reagent in the glycidol formation and accelerates its subsequent conversion to glycerol.
- Dmitriev,Zanaveskin,Khadzhiev
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p. 1627 - 1630
(2018/11/21)
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- Preparation method of 1,3-dihydroxyacetone
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The invention relates to the technical field of organic synthesis, and discloses a preparation method of 1, 3-dihydroxyacetone. The preparation method of 1,3-dihydroxyacetone comprises the following steps: (1) carrying out contact reaction between glycerol and halogenated reagents in presence of a catalyst to prepare 1,3-dichloro-2-propanol; (2) carrying out oxidative dehydrogenation reaction on the 1,3-dichloro-2-propanol to obtain an intermediate product 1,3-dichloro-2 acetone; (3) contacting the 1,3-dichloro-2 acetone with alkali substances in a water-containing medium for hydrolysis reaction to obtain the 1,3-dihydroxyacetone, wherein a hydrolysis reaction temperature is 25 to 60 DEG C. According to the preparation method of the 1,3-dihydroxyacetone, the conversion rate of the glycerol and the yield of the 1,3-dihydroxyacetone are higher; by taking zirconium oxide as the catalyst, the preparation method disclosed by the invention is high-efficient, is low in cost and has industrial application prospect.
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Paragraph 0047; 0048
(2017/10/26)
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- A safer and greener chlorohydrination of allyl chloride with H2O2 and HCl over hollow titanium silicate zeolite
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Industrial production of dichloropropanols through chlorohydrination of allyl chloride suffers from a series of disadvantages such as use of hazardous Cl2, low atom economy, low dichloropropanol concentration and serious pollution. In this work, a safer and greener route for chlorohydrination of allyl chloride with H2O2 and HCl over hollow titanium silicate (HTS) at mild condition is developed. Unlike the traditional Cl2-based chlorohydrination, this novel method is initiated via synergistic effect of Lewis acidity (HTS) and Br?nsted acidity (HCl) to promote occurrence of oxidation, protonation and nucleophilic reaction of allyl chloride simultaneously and hence dichloropropanols are generated. Owing to a completely different reaction route, the formation of 1,2,3-trichloropropane by-product is depressed and the content of dichloropropanol exceeded 22?wt%, which increase by about 4 times compared with traditional Cl2-based chlorohydrination (the content of dichloropropanol is below 4?wt%). At the optimized conditions, both of the allyl chloride conversion and dichloropropanol selectivity could approach 99% simultaneously and the waste is minimized. What's more, the HTS was reusable. Concentrated HCl solution treatment was adopted to test HTS's stability. The characterization and catalytic evaluation results reveal that, although parts of the framework Ti species have transformed into non-framework Ti and then leached into the solution, HTS remains structural stable, and the allyl chloride conversion and dichloropropanol selectivity didn't decrease obviously during the treatment.
- Peng, Xinxin,Xia, Changjiu,Lin, Min,Shu, Xingtian,Zhu, Bin,Wang, Baorong,Zhang, Yao,Luo, Yibin,Mu, Xuhong
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- Method for comprehensive utilization of hexachloroethane
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The invention relates to a comprehensive utilization method of a dichloroethane chlorination byproduct namely hexachloroethane. The comprehensive utilization method comprises the following steps: adding a hexachloroethane solution, glycerin, a hydrogenation catalyst and a chlorination catalyst into a high-pressure kettle; after feeding is finished, performing hydrodechlorination and glycerin chlorination reaction at the same time at certain temperature and under certain hydrogen pressure; after reaction is finished, maintaining the temperature for 4h, and then reducing the temperature to the room temperature; performing filtering separation to obtain the hydrogenation catalyst, layering reaction liquid to obtain a solvent layer and a glycerin layer, wherein the solvent layer contains a solvent, pentachloroethane, pentachloroethane and trichloroethane, and the glycerin layer contains the glycerin, dichloropropanol, water, the chlorination catalyst and monochlorohydrin.
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Paragraph 0015; 0017-0019; 0021; 0023; 0025; 0027; 0030
(2017/10/27)
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- Chlorohydrination of allyl chloride with HCl and H2O2 catalyzed by hollow titanium silicate zeolite to produce dichloropropanol
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Overall, over 95% of epichlorohydrin is industrially manufactured via the chlorohydrination route with hazardous Cl2 as a reagent, which brings serious operation and pollution problems. Herein, we describe a novel Cl2-free process for the synthesis of dichloropropanols from allyl chloride with H2O2 and HCl catalyzed by hollow titanium silicate zeolite under mild conditions. A high conversion and overall dichloropropanol selectivity exceeding 95% are simultaneously achieved, and the heterogeneous catalyst is highly stable and amenable for reuse. Comprehensive experimental and spectroscopic data suggest that the Lewis acidity of the framework Ti species has a synergistic effect with the Br?nsted acidity of HCl that promotes the epoxidation of allyl chloride and the ring opening of the epoxy groups.
- Peng, Xinxin,Xia, Changjiu,Lin, Min,Yuan, Hui,Zhu, Bin,Zhang, Yao,Wang, Baorong,Shu, Xingtian
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supporting information
p. 1221 - 1225
(2017/08/15)
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- Trihaloisocyanuric Acid/Triphenylphosphine: An Efficient System for Regioselective Conversion of Epoxides into Vicinal Halohydrins and Vicinal Dihalides under Mild Conditions
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A new synthetic method has been developed for the regioselective conversion of epoxides to vicinal chloro-/bromohydrins and vicinal dihalides by reaction with the system trihaloisocyanuric acid/tri?phenylphosphine in acetonitrile under mild and neutral conditions. The reactions proceed smoothly in high yield at room temperature and at reflux, respectively, over a short time.
- De Andrade, Vitor S. C.,De Mattos, Marcio C. S.
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p. 1381 - 1388
(2016/05/19)
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- 1,1 the [...] -di-alkyl -3,3 the [...] -(2-phosphate ester -1,3-propyl) imidazole in the process for the preparation of salt compound
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The invention relates to a 1,1'-dialkyl-3,3'-(2-phosphate-1,3-propylidene)imidazolium compound and a preparation method thereof. The structural formula of the 1,1'-dialkyl-3,3'-(2-phosphate-1,3-propylidene)imidazolium compound is shown in the specification, wherein n is 6, 8, 10, 12 and 14, and the alkyl imidazole can be replaced with alkyl benzimidazole. The 1,1'-dialkyl-3,3'-(2-phosphate-1,3-propylidene)imidazolium is a amphoteric dimeric surfactant, and a concrete synthesis method comprises the following steps: synthesizing 1, 3-dichloro-2-propanol, synthesizing N-alkyl imidazole, synthesizing 1,1'-dialkyl-3,3'-(2-hydroxyl-1,3-propylidene)imidazole hydrochloride, and synthesizing 1,1'-dialkyl-3,3'-(2-phosphate-1,3-propylidene)imidazolium. The 1,1'-dialkyl-3,3'-(2-phosphate-1,3-propylidene)imidazolium compound and the preparation method are easily available in raw materials, the reaction technology conditions are easy to control, operation is simple, the product is easy to purify, and yield is high. The compound has low critical micelle concentration, and can be used as a wetting agent, an emulsifier, a foaming agent and a foam stabilizer. A molecular structure has macrocyclic cefpimizole group and phosphate ester, and thus the compound has good thermal stability, solubility, salinity resistance, temperature resistance and acid and base resistance.
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Paragraph 0036; 0037
(2016/12/07)
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- A simplified early stage assessment of process intensification: Glycidol as a value-added product from epichlorohydrin industry wastes
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The present work deals with the production of glycidol through a new synthetic approach based on the conversion of 2-chloro-1,3-propanediol (β-MCH), a by-product in the epichlorohydrin production plant. β-MCH was converted with high yield (90%) and selectivity (99%) to glycidol using an alcoholic solution of KOH at room temperature in only 30 minutes. A simplified early stage assessment based on the use of the green metrics and a life cycle analysis were adopted in order to evaluate the environmental feasibility of this innovative route if compared with the traditional chain to epichlorohydrin. The waste recovery and the maximization of the overall process efficiency lead to sensible reductions per each indicator considered in the assessment, suggesting the possibility of developing on a full industrial scale. In addition, in order to verify the potentialities behind the substitution of the fossil-based glycidol with the product resulted from the recovery of the β-MCH, a cradle-to-gate analysis and the GREENMOTION tool were adopted.
- Cespi,Cucciniello,Ricciardi,Capacchione,Vassura,Passarini,Proto
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supporting information
p. 4559 - 4570
(2016/08/18)
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- PROCESS FOR HYDROGENATING DICHLOROISOPROPYL ETHER
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Convert dichloroisopropyl ether into a halogenated derivative by contacting the dichloroisopropyl ether with a source of hydrogen and a select heterogeneous hydrogenation catalyst under process conditions selected from a combination of a temperature within a range of from 50 degrees centigrade (oC) to 350 oC, a pressure within a range of from atmospheric pressure (0.1 megapascals) to 1000 pounds per square inch (6.9 MPa), a liquid feed volume flow to catalyst mass ratio between 0.5 and 10 L/Kg*h and a volume hydrogen / volume liquid ratio between 100 and 5000 ml gas/ ml liquid. The halogenated derivative is at least one of 1-chloro-2-propanol and 1,2-dichloropropane 1, and glycerin monochlorohydrin.
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Page/Page column 6
(2016/04/20)
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- A modified L-shaped molecular sieve catalytic glycerin method of preparing dichlorohydrine chloride
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The invention provides a method for preparing dichloropropanol by modified L-type molecular sieve catalyst-catalytic chlorination of glycerin. Biodiesel by-product glycerin and HCl gas as raw materials undergo a reaction at a temperature of 110-140 DEG C in the presence of a self-made modified L-type molecular sieve catalyst to produce dichloropropanol. The method for preparing dichloropropanol has a low raw material cost, mild reaction conditions, less side products and high industrial application values. Through use of the modified L-type molecular sieve LaHL-5 catalyst prepared by crystallization at a crystallization temperature of 120 DEG C for crystallization time of 96h, after a chlorination reaction at a temperature of 130 DEG C for 10h, a total dichloropropanol yield is 95.87%.
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Paragraph 0025-0028
(2017/03/18)
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- A kind of glycerin method of preparing dichlorohydrine chloride
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The invention relates to a method of preparing dichloropropanol by glycerol chlorination, belonging to the field of application of biomas glycerol. The method comprises the following step of: by using a hydrogen chloride gas as a chlorinating agent, by using malic acid, citric acid and lactic acid as a catalyst to catalyze glycerol chlorination to prepare the dichloropropanol. The material glycerol adopted by the method disclosed by the invention is cheap in price, and chloridized to have important industrial significance in developing downstream products. Hydroxyl carboxylic acid is easy to obtain and does not need further treatment; while being used as the catalyst for chlorination, the hydroxyl carboxylic acid has no pollution to environment, is high in catalytic activity, simple in process, gentle in reaction condition, less in dosage of the catalyst and less in reaction byproducts.
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Paragraph 0021-0023
(2017/05/12)
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- PROCESS FOR THE PRODUCTION OF DICHLOROHYDRONS
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This invention is related to the process of dichlorohydrins production starting from glycerol by hydrochlorination with hydrochloric acid in the presence of a new class of catalysts consisting in the acyl chlorides.
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Page/Page column 23; 24
(2015/03/28)
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- CONVERSION OF GLYCERINE TO DICHLOROHYDRINS AND EPICHLOROHYDRIN
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The present invention relates to a process for the production of dichlorohydrin by catalyzed hydrochlorination of glycerine where the reaction is performed in at least two subsequent stages operating continuously at different pressures with both vapor and liquid recycle. The first reactor, low pressure (L. P.) reactor, operating at a pressure ranging from 1 to 4 bar and at a temperature from 900C to 1300C converts most of GLY to MHC. The second reactor, medium pressure (M. P. ) reactor, operating at a pressure ranging from 5 to 20 bar and at temperature from 90 °c to 1300C converts the effluent from the L. P. reactor to DCH with an adequate degree of conversion. Each reactor is followed by a stripping unit.
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Paragraph 0078-0081; 0088-0092
(2017/01/02)
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- 1,3,2,4-diazadiphosphetidine-based phosphazane oligomers as source of P(III) atom economy reagents: Conversion of epoxides to vic -haloalcohols, vic -dihalides, and alkenes in the presence of halogen sources
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1,3,2,4-Diazadiphosphetidines (P1-P3), as easily prepared, stable, and heterogeneous P(III) compounds, were used for the efficient conversion of epoxides to vic-halohydrins, vic-dihalides, or alkenes in the presence of different halogen sources in CH3CN. Of these phosphazanes, P3 is most suitable and contains 4 phosphorous atoms with the advantage of having greater atom economy and its phosphorus oxide byproduct can be easily separated from the reaction mixture by simple filtration. The nitrogen atoms in this molecule can also act as acid scavengers in the reaction.
- Iranpoor, Nasser,Firouzabadi, Habib,Etemadidavan, Elham
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p. 1165 - 1173
(2014/10/16)
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- Synthesis of Di-, Tri-, and tetrasubstituted oxetanes by rhodium-catalyzed O-H insertion and C-C bond-forming cyclization
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Oxetanes offer exciting potential as structural motifs and intermediates in drug discovery and materials science. Here an efficient strategy for the synthesis of oxetane rings incorporating pendant functional groups is described. A wide variety of oxetane 2,2-dicarboxylates were accessed in high yields, including functionalized 3-/4-aryl-and alkyl-substituted oxetanes and fused oxetane bicycles. Enantioenriched alcohols provided enantioenriched oxetanes with complete retention of configuration. The oxetane products were further derivatized, while the ring was maintained intact, thus highlighting their potential as building blocks for medicinal chemistry.
- Davis, Owen A.,Bull, James A.
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supporting information
p. 14230 - 14234
(2015/02/19)
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- A convenient method for producing mono- and dichlorohydrins from glycerol
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A new method for the transformation of glycerol into mono- and dichlorohydrins has been studied. With trimethylchlorosilane as chlorinating agent and acetic acid as catalyst, mono- and dichlorohydrins have been obtained in high yields and selectivity. In fact, under different reaction conditions, the synthesis of α-monochlorohydrin (3-chloropropan-1,2-diol) or α,γ-dichlorohydrin (1,3-dichloropropan-2-ol) as predominant product has been achieved. This process was also exploited for the valorisation of the crude mixture of glycerol and monochlorohydrin (glyceric mixture), a by-product from an earlier BioDiesel production. A reaction mechanism has been proposed based on investigations on the chlorination of different alcohols.
- Giomi, Donatella,Malavolti, Marino,Piccolo, Oreste,Salvini, Antonella,Brandi, Alberto
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p. 46319 - 46326
(2015/02/19)
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- METHOD FOR PREPARING CHLOROHYDRINS AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS PREPARED THEREBY
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A method of preparing chlorohydrins and a method of preparing epichlorohydrin by using chlorohydrins prepared using the method are provided. The method of preparing chlorohydrins by reacting polyhydroxy aliphatic hydrocarbon with a chlorination agent in the presence of a catalyst includes at least one combination of a series of unit operations including a first reaction step, a water removal step, and a second reaction step, in that respective order, and after mixing at least a portion of a reaction mixture discharged from at least one reaction steps from among the plurality of reaction steps with an additional chlorination agent, recirculating the resulting mixture to the reaction step from which the reaction mixture was discharged. The method of preparing epichlorohydrin includes a step of reacting chlorohydrins prepared using the method of preparing chlorohydrins, with an alkaline agent.
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Paragraph 0105-0106
(2013/04/13)
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- METHOD FOR PREPARING CHLOROHYDRINS AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS PREPARED THEREBY
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A method of preparing chlorohydrins and a method of preparing epichlorohydrin by using chlorohydrins prepared using the method are provided. The method of preparing chlorohydrins by reacting polyhydroxy aliphatic hydrocarbon with a chlorination agent in the presence of a catalyst includes at least one combination of a series of unit operations including a first reaction step, a water removal step, and a second reaction step, in that respective order, wherein the method further includes purifying chlorohydrins from a reaction mixture discharged from a final reaction step of the plurality of reaction steps. The method of preparing epichlorohydrin includes reacting chlorohydrins prepared using the method of preparing chlorohydrins, with an alkaline agent.
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Paragraph 0105-0106
(2013/04/24)
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- METHOD FOR PREPARING CHLOROHYDRINS COMPOSITION AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS COMPOSITION PREPARED THEREBY
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Disclosed are a method for preparing chlorohydrins composition and a method for preparing epichlorohydrin using chlorohydrins prepared thereby. The disclosed method for preparing chlorohydrins composition reacts polyhydroxy aliphatic hydrocarbon with a chlorination agent in the presence of a catalyst, comprises at least one combination of a series of unit operations including a first reaction step, a water removal step, and a second reaction step in the respective order, and additionally comprises a step for reacting the chlorohydrins composition derived from a plurality of reaction mixtures discharged from the plurality of reaction steps with an alkaline chemical, and removing the catalyst included in the chlorohydrins composition in the form of an alkali metal salt. The disclosed method for preparing epichlorohydrin includes a step for contacting the chlorohydrins composition, which was prepared using the method for preparing chlorohydrins composition, with an alkaline chemical.
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Paragraph 0103-0104
(2013/05/08)
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- METHOD FOR PREPARING CHLOROHYDRINS COMPOSITION AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS COMPOSITION PREPARED THEREBY
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Provided are a method of preparing a chlorohydrin composition and a method of preparing epichlorohydrin by using a chlorohydrin composition prepared by using the method. The method of preparing chlorohydrins in which polyhydroxy aliphatic hydrocarbon is reacted with a chlorination agent in the presence of a catalyst includes performing at least one combination of a series of unit operations comprising a first reaction step, a water removal step, and a second reaction step in this stated order, wherein the method further includes mixing a chlorohydrin concentrate obtained by purifying the reaction mixture discharged from the final reaction step from among the reaction steps and a water-rich layer discharged from the water-removal step and diluting the mixture with water. The method of preparing epichlorohydrin includes contacting the chlorohydrin composition prepared by using the method of preparing a chlorohydrin composition with an alkaline agent.
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Paragraph 0101-0102
(2013/05/08)
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- METHOD FOR PREPARING CHLOROHYDRINS AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS PREPARED THEREBY
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A method of preparing chlorohydrins and a method of preparing epichlorohydrin using chlorohydrins prepared by using the same method are provided. The method is to prepare chlorohydrins by reacting polyhydroxy aliphatic hydrocarbon with a chlorination agent in the presence of a catalyst, and the method includes at least one combination of a series of unit operations including the following steps in the following stated order: a first reaction step; a water removal step; and a second reaction step, wherein the water removing step is performed by distillation operation based on a boiling point difference between constituents of a reaction mixture. The method of preparing epichlorohydrin includes reacting chlorohydrins prepared by using the method of preparing chlorohydrins with an alkaline agent.
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Paragraph 0101-0103
(2013/05/08)
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- METHOD FOR PREPARING CHLOROHYDRINS COMPOSITION AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS COMPOSITION PREPARED THEREBY
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A method of preparing a chlorohydrin composition and a method of preparing epichlorohydrin by using a chlorohydrin composition prepared by using the method are provided. The method of preparing a chlorohydrin composition in which a polyhydroxy aliphatic hydrocarbon is reacted with a chlorination agent in the presence of a catalyst includes performing at least one combination of a series of unit operations comprising a first reaction step, a water removal step, and a second reaction step in this stated order, wherein the method further includes mixing a chlorohydrin concentrate obtained by purifying the reaction mixture discharged from the final reaction step from among the plurality of reaction steps and a water-rich layer discharged from the water-removal step. The method of preparing epichlorohydrin includes contacting the chlorohydrin composition prepared by using the method of preparing a chlorohydrin composition with an alkaline agent
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Paragraph 0099-0100
(2013/05/08)
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- METHOD FOR PREPARING CHLOROHYDRINS AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS PREPARED THEREBY
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A method of preparing chlorohydrins and a method of preparing epichlorohydrin by using chlorohydrins prepared using the method are provided. The method of preparing chlorohydrins by reacting polyhydroxy aliphatic hydrocarbon with a chlorination agent in the presence of a catalyst includes at least one combination of a series of unit operations including a first reaction step, a water removal step, and a second reaction step, in that respective order, wherein the method further includes purifying chlorohydrins from a reaction mixture discharged from a final reaction step of the plurality of reaction steps. The method of preparing epichlorohydrin includes reacting chlorohydrins prepared using the method of preparing chlorohydrins, with an alkaline agent.
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Paragraph 0102-0103
(2013/05/22)
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- METHOD FOR PREPARING CHLOROHYDRINS AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS PREPARED THEREBY
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A method of preparing chlorohydrins and a method of preparing epichlorohydrin using chlorohydrins prepared by using the same method are provided. The method is to prepare chlorohydrins by reacting polyhydroxy aliphatic hydrocarbon with a chlorination agent in the presence of a catalyst, and the method includes at least one combination of a series of unit operations including the following steps in the following stated order: a first reaction step; a water removal step; and a second reaction step, wherein the water removing step is performed by distillation operation based on a boiling point difference between constituents of a reaction mixture. The method of preparing epichlorohydrin includes reacting chlorohydrins prepared by using the method of preparing chlorohydrins with an alkaline agent.
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Paragraph 0101-0102
(2013/05/22)
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- METHOD FOR PREPARING CHLOROHYDRINS COMPOSITION AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS COMPOSITION PREPARED THEREBY
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A method of preparing a chlorohydrin composition and a method of preparing epichlorohydrin by using a chlorohydrin composition prepared by using the method are provided. The method of preparing a chlorohydrin composition in which a polyhydroxy aliphatic hydrocarbon is reacted with a chlorination agent in the presence of a catalyst includes performing at least one combination of a series of unit operations comprising a first reaction step, a water removal step, and a second reaction step in this stated order, wherein the method further includes mixing a chlorohydrin concentrate obtained by purifying the reaction mixture discharged from the final reaction step from among the plurality of reaction steps and a water-rich layer discharged from the water-removal step. The method of preparing epichlorohydrin includes contacting the chlorohydrin composition prepared by using the method of preparing a chlorohydrin composition with an alkaline agent
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Paragraph 0099-0100
(2013/05/22)
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- PROCESS FOR THE CHLORINATION OF A HYDROXYLATED ORGANIC COMPOUND
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Process for the chlorination of an organic compound comprising at least one aliphatic hydroxyl group, said process comprising the steps of actively adding to said organic compound (i) hydrogen chloride and (ii) a HCl desolubilizer or a precursor thereof, and heating the resulting mixture at a reaction temperature in the range 20°-160°C, wherein said chlorination is performed in the presence of a catalyst selected from the group consisting of (a) ketones, (b) aldehydes, (c) carboxylic acids with 1-8 carbon atoms, (d) organic compounds comprising a β-diketone moiety or a β-keto aldehyde moiety, and (e) organic polymers comprising at least one carbonyl group, having a vapour pressure at the reaction temperature of less than 1 mbar, a weight average molecular weight Mw of 500 g/mole or more, and are soluble in the reaction mixture at the reaction temperature, and wherein the HCl desolubilizer is an alkali metal chloride salt, an alkaline earth metal chloride salt, or an acid.
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Page/Page column 17; 18
(2013/03/26)
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- METHOD FOR PRODUCTION OF DICHLOROPROPANOLS FROM GLYCEROL
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Method for production of dichloropropanols from glycerol using continuous method, in the presence of acetic acid as a catalyst, with the catalyst concentration in the reacting mass varying in the range of 0.0005 to 0.007 mol/L, and the process of hydrochlorina? tion is carried out in the temperature range from 80 to 160°C, consists in the fact that hydrochlorination of glycerol is carried out in two stages, while in the first stage, glycer? ol is subjected to wet hydrochlorination using hydrochloric acid contained in the stream of acidic dichloropropanols, then the post-reaction mass from the first stage of hydro? chlorination is directed to a reactive column, in which completing the reaction of resi? dues of dissolved hydrogen chloride is carried out, as well as separation of the post- reaction mixture to stream of diluted dichloropropanols and decoction stream, which is directed to the second stage of dry hydrochlorination under pressure with gaseous hy? drogen chloride; after the second stage of hydrochlorination, the post-reaction mixture is directed to a distillation column, in which dewatering is carried out, while the distillate from the distillation column is directed to the first stage of glycerol hydrochlorination as a stream of acidic dichloropropanols, and the decoction being a stream of concentrated dichloropropanols is subjected to rectification.
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Page/Page column 9-10
(2012/07/28)
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- Protective opening of epoxide using pivaloyl halides under catalyst-free conditions
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An efficient and environmentally benign protocol for protective opening of epoxide (POE) with pivaloyl halides in solvent-free conditions and in aqueous media under catalyst-free conditions has been developed. The green reaction conditions, simple work-up procedures, high yields and broad scope of the reaction illustrate the good synthetic utility of this method. The key advantages of the reaction are regioselectivity and reconvertability of products into their prior epoxides in the presence of mild reaction conditions.
- Rao, Chitturi Bhujanga,Rao, Dasireddi Chandra,Venkateswara, Mallem,Venkateswarlu, Yenamandra
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supporting information; experimental part
p. 2704 - 2707
(2011/12/05)
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- A PROCESS FOR THE PREPARATION OF DICHLOROHYDRIN
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A process for the preparation of dichlorohydrin starting from isobutylene and glycerol is disclosed. Th used glycerol can be derived, as a byproduct, from the transesterification of triglycerides. Dichlorohydrin is produced in a cyclic process, wherein, by reaction of isobutylene and glycerol, mono tert. butyl ether is formed, which is thereafter reacted with hydrogen chloride to produce the desired dichlorohydrin. The byproducts, formed in each step, can be recycled to the first step of the process.
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Page/Page column title page; 4
(2011/08/21)
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- METHOD OF PREPARING CHLOROHYDRINS BY REACTING POLYHYDROXY ALIPHATIC HYDROCARBON WITH CHLORINATION AGENT
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A method of preparing chlorohydrins from polyhydroxy aliphatic hydrocarbon such as glycerol. The method includes irradiating an ultrasonic wave to a reaction mixture during reaction.
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Paragraph 58-60
(2011/02/24)
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- METHOD OF PREPARING DICHLOROPROPANOL USING GLYCEROL WITH IMPROVED SELECTIVITY FOR DICHLOROPROPANOL
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A method of preparing dichloropropanol using glycerol. The method includes: chlorination of glycerol including a plurality of chlorination reaction stages using a catalyst; and a water-removing stage performed between the reaction stages, independently of the reaction stages.
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Page/Page column 2; 4
(2011/11/30)
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- Polyfluoroalloxy phosphonic and phosphinic acid derivatives: I. 1-Hydroxy-2,2,2-trichloroethylphosphinates
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Polyfluoroalkyl esters of 1-hydroxy-2,2,2-trichloroethylphosphonic and aryl(alkyl-)phosphinic acids exhibited antienzyme activity towards esterases of animal and microbial origin. A good correlation is observed between high antiesterase activity of the target compounds and their physicochemical parameters, characterizing their structure.
- Krutikova,Krutikov,Erkin
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scheme or table
p. 428 - 433
(2010/08/04)
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- Investigation of the kinetics and mechanism of the glycerol chlorination reaction using gas chromatography-mass spectrometry
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As a primary by-product in biodiesel production, glycerol can be used to prepare an important fine chemical, epichlorohydrin, by the glycerol chlorination reaction. Although this process has been applied in industrial production, unfortunately, less attention has been paid to the analysis and separation of the compounds in the glycerol chlorination products. In this study, a convenient and accurate method to determine the products in glycerol chlorination reaction was established and based on the results the kinetic mechanism of the reaction was investigated. The structure of main products, including 1,3-dichloropropan-2-ol, 2,3-dichloropropan-1-ol, 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol and glycerol was ascertained by gas chromatography-mass spectrometry and the isomers of the products were distinguished. Apidic acid was considered as the best catalyst because of its excellent catalytic effect and high boiling point. The mechanism of the glycerol chlorination reaction was proposed and a new kinetic model was developed. Kinetic equations of the process in the experimental range were obtained by data fitting and the activation energies of each tandem reaction were 30.7, 41.8, 29.4 and 49.5 kJ mol-1, respectively. This study revealed the process and mechanism of the kinetics and provides the theoretical basis for engineering problems. 2009 copyright (CC) SCS.
- Ling, Xiuquan,Lu, Dingqiang,Wang, Jun,Liang, Mingxin,Zhang, Shumin,Ren, Wei,Chen, Jianhui,Ouyang, Pingkai
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experimental part
p. 101 - 112
(2010/11/05)
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- Convenient synthesis of chlorohydrins from epoxides using zinc oxide: Application to 5,6-epoxysitosterol
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Efficient synthesis of protected and unprotected chlorohydrins has been achieved by ring opening of epoxides with acetyl/benzoyl chloride and TMSCl using a catalytic amount of ZnO as a reusable catalyst. The applicability of ZnO is further extended by performing the cleavage of the natural product 5,6-epoxysitosterol with acetyl chloride.
- Moghaddam, Firouz Matloubi,Saeidian, Hamdollah,Mirjafary, Zohreh,Javan, Marjan Jebeli,Farimani, Mehdi Moridi,Seirafi, Marjan
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experimental part
p. 157 - 163
(2009/09/30)
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- Facile, high regio- And chemoselective conversion of epoxides to β-chlorohydrins using chlorodiphenylphosphine under solvent-free conditions
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A new method is described for the mild and high regioselective conversion of epoxides to β-chlcrohydrins in high yields even in the presence of alcohols, carboxylic acids, oximes, amides, thiols and tetrahydropyranyl ethers using chlorodiphenylphosphine (ClPPh2) under solvent-free and neutral conditions at room temperature and in short reaction times. In addition, some other functional groups such as carbon-carbon double bonds, ester groups and also phenyl ring that are present in the epoxide molecules remain intact in this method.
- Aghapour, Ghasem,Afzali, Asieh,Salek, Fahimeh
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experimental part
p. 231 - 236
(2009/12/03)
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- PROCESS FOR THE PREPARATION OF A DICHLOROPROPANOL PRODUCT
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The present invention relates to a process for the preparation of a dichloropropanol product, wherein the dichloropropanol product comprises a mixture of 1,2-dichloropropan-3-ol and 1,3-dichloropropan-2-ol, said process comprising the steps of: (a) contacting glycerol with hydrochloric acid in a molar ratio of glycerol to hydrochloric acid of about less than 1 to about 100 to form a first product mixture comprising l-chloropropane-2,3-diol as a major constituent; and (b) contacting said first product mixture comprising 1-chloropropane-2,3-diol as a major constituent with hydrochloric acid in a molar ratio of 1-chloropropane-2,3- diol to hydrochloric acid of about less than 1 to about 100 to form the dichloropropanol product.
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Page/Page column 15
(2009/10/18)
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- Process for the Production of Alpha, Gamma-Dichlorohydrin From Glycerin and Hydrochloric Acid
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A process for preparing α,γ-dichlorohydrin starting from glycerin and preferably gaseous anhydrous hydrochloric acid in the presence of low-volatility organic acids as catalysts.
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Page/Page column 3
(2009/04/24)
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- PROCESS FOR PREPARING CHLOROHYDRIN BY REACTION OF POLYOL WITH HYDROCHLORIC ACID
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The present invention relates to a method for preparing chlorohydrin by chlorination of polyol such as glycerin with hydrogen chloride. The method of the present invention is composed of the following processes: reaction mixture feed comprising polyol, hydrogen chloride and organic acid (catalyst for chlorination) is loaded into the first reactor, in which chlorohydrin is generated by chlorination; the first product mixture feed containing the chlorohydrin and non- reacted reaction mixture discharged from the first reactor and the additional polyol feed are supplied to the second reactor, in which chlorohydrin is generated by additional chlorination; the second product mixture feed containing the chlorohydrin discharged from the second reactor is loaded in distillation column and then distillation product containing chlorohydrin is separated through the top of the distillation column; and some re-circulated feed of distillation residual solution containing chlorohydrin, is re-circulated into the first reactor.
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Page/Page column 40-46
(2009/05/29)
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- METHOD OF PREPARING DICHLOROPROPANOL FROM GLYCEROL IN THE PRESENCE OF HETEROPOLYACID CATALYST AND/OR ABSORBENT UNDER SOLVENT-FREE CONDITIONS
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Provided is a method of preparing dichloropropanol from glycerol. The method includes reacting glycerol with a chlorinating agent, and the reaction is performed in the presence of a heteropolyacid catalyst and/or an absorbent under solvent-free conditions. Thus, according to the method, dichloropropanol can be directly prepared from glycerol. Since a solvent is not used, a process of removing the solvent is not necessary, and thus the volume of a reactor can be reduced. In addition, conventional problems such as recovery of the catalyst and separation of an azeotropic mixture including the catalyst and products can be overcome. In addition, expensive dichloropropanol can be produced at high yield from inexpensive glycerol.
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Page/Page column 9-10
(2010/01/07)
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- METHOD OF PREPARING DICHLOROPROPANOL FROM GLYCEROL USING HETEROPOLYACID CATALYSTS
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Provided is a method of preparing dichloropropanol from glycerol. According to the method, glycerol is reacted with a chlorinating agent using a heteropolyacid catalyst to prepare dichloropropanol. Accordingly, dichloropropanol can be directly prepared from glycerol by using heteropolyacid catalysts, and conventional problems such as recovery of the catalyst and separation of an azeotropic mixture including the catalyst and the products can be overcome. In addition, since the catalyst can be easily recovered and reused, the manufacturing process can be simplified and expensive dichloropropanol can be produced at high yield from inexpensive glycerol.
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Page/Page column 6-7; 8
(2009/07/17)
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- One-way biohydrogen transfer for oxidation of sec-alcohols
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(Chemical Equation Presented) Quasi-irreversible oxidation of sec-alcohols was achieved via biocatalytic hydrogen transfer reactions using alcohol dehydrogenases employing selected ketones as hydrogen acceptors, which can only be reduced but not oxidized. Thus, only 1 equiv of oxidant was required instead of a large excess. For the oxidation of both isomers of methylcarbinols a single nonstereoselective short-chain dehydrogenase/reductase from Sphingobium yanoikuyae was identified and overexpressed in E. coli.
- Lavandera, Ivan,Kern, Alexander,Resch, Verena,Ferreira-Silva, Bianca,Glieder, Anton,Fabian, Walter M. F.,De Wildeman, Stefaan,Kroutil, Wolfgang
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supporting information; experimental part
p. 2155 - 2158
(2009/05/27)
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- MANUFACTURE OF DICHLOROPROPANOL
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Manufacture of dichloropropanol Process for manufacturing dichloropropa nol wherein a glycerol-based product comprising at least one diol containi ng at least 3 carbon atoms other than 1,2- propanediol, is reacted with a chlorinati ng agent, and of products derived from dichloropropanol such as ep ichlorohydrin and epoxy resins. No figure.
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Page/Page column 19-21
(2009/03/07)
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